Applying shot boundary detection for automated crystal growth analysis during in situ transmission electron microscope experiments.

In situ scanning transmission electron microscopy is being developed for numerous applications in the study of nucleation and growth under electrochemical driving forces. For this type of experiment, one of the key parameters is to identify when nucleation initiates. Typically, the process of identifying the moment that crystals begin to form is a manual process requiring the user to perform an observation and respond accordingly (adjust focus, magnification, translate the stage, etc.). However, as the speed of the cameras being used to perform these observations increases, the ability of a user to "catch" the important initial stage of nucleation decreases (there is more information that is available in the first few milliseconds of the process). Here, we show that video shot boundary detection can automatically detect frames where a change in the image occurs. We show that this method can be applied to quickly and accurately identify points of change during crystal growth. This technique allows for automated segmentation of a digital stream for further analysis and the assignment of arbitrary time stamps for the initiation of processes that are independent of the user's ability to observe and react.

Observation and quantification of nanoscale processes in lithium batteries by operando electrochemical (S)TEM.

An operando electrochemical stage for the transmission electron microscope has been configured to form a "Li battery" that is used to quantify the electrochemical processes that occur at the anode during charge/discharge cycling. Of particular importance for these observations is the identification of an image contrast reversal that originates from solid Li being less dense than the surrounding liquid electrolyte and electrode surface. This contrast allows Li to be identified from Li-containing compounds that make up the solid-electrolyte interphase (SEI) layer. By correlating images showing the sequence of Li electrodeposition and the evolution of the SEI layer with simultaneously acquired and calibrated cyclic voltammograms, electrodeposition, and electrolyte breakdown processes can be quantified directly on the nanoscale. This approach opens up intriguing new possibilities to rapidly visualize and test the electrochemical performance of a wide range of electrode/electrolyte combinations for next generation battery systems.

Factors influencing quantitative liquid (scanning) transmission electron microscopy.

One of the experimental challenges in the study of nanomaterials in liquids in the (scanning) transmission electron microscope ((S)TEM) is gaining quantitative information. A successful experiment in the fluid stage will depend upon the ability to plan for sensitive factors such as the electron dose applied, imaging mode, acceleration voltage, beam-induced solution chemistry changes, and the specifics of solution reactivity. In this paper, we make use of a visual approach to show the extent of damage of different instrumental and experimental factors in liquid samples imaged in the (S)TEM. Previous results as well as new insights are presented to create an overview of beam-sample interactions identified for changing imaging and experimental conditions. This work establishes procedures to understand the effect of the electron beam on a solution, provides information to allow for a deliberate choice of the optimal experimental conditions to enable quantification, and identifies the experimental factors that require further analysis for achieving fully quantitative results in the liquid (S)TEM.

Interfacial ferromagnetism in LaNiO3/CaMnO3 superlattices.

We observe interfacial ferromagnetism in superlattices of the paramagnetic metal LaNiO3 and the antiferromagnetic insulator CaMnO3. LaNiO3 exhibits a thickness dependent metal-insulator transition and we find the emergence of ferromagnetism to be coincident with the conducting state of LaNiO3. That is, only superlattices in which the LaNiO3 layers are metallic exhibit ferromagnetism. Using several magnetic probes, we have determined that the ferromagnetism arises in a single unit cell of CaMnO3 at the interface. Together these results suggest that ferromagnetism can be attributed to a double exchange interaction among Mn ions mediated by the adjacent itinerant metal.

Interfacial ferromagnetism and exchange bias in CaRuO3/CaMnO3 superlattices.

We have found ferromagnetism in epitaxially grown superlattices of CaRuO(3)/CaMnO(3) that arises in one unit cell at the interface. Scanning transmission electron microscopy and electron energy loss spectroscopy indicate that the difference in magnitude of the Mn valence states between the center of the CaMnO(3) layer and the interface region is consistent with double exchange interaction among the Mn ions at the interface. Polarized neutron reflectivity and the CaMnO(3) thickness dependence of the exchange bias field together indicate that the interfacial ferromagnetism is only limited to one unit cell of CaMnO(3) at each interface. The interfacial moment alternates between the 1 µ(B)/interface Mn ion for even CaMnO(3) layers and the 0.5 µ(B)/interface Mn ion for odd CaMnO(3) layers. This modulation, combined with the exchange bias, suggests the presence of a modulating interlayer coupling between neighboring ferromagnetic interfaces via the antiferromagnetic CaMnO(3) layers.

Investigating the electronic structure of fluorite-structured oxide compounds: comparison of experimental EELS with first principles calculations.

Energy loss spectra from fluorite-structured ZrO(2), CeO(2), and UO(2) compounds are compared with theoretical calculations based on density functional theory (DFT) and its extensions, including the use of Hubbard-U corrections (DFT + U) and hybrid functionals. Electron energy loss spectra (EELS) were obtained from each oxide using a scanning transmission electron microscope (STEM). The same spectra were computed within the framework of the full-potential linear augmented plane-wave (FLAPW) method. The theoretical and experimental EEL spectra are compared quantitatively using non-linear least squares peak fitting and a cross-correlation approach, with the best level of agreement between experiment and theory being obtained using the DFT + U and hybrid computational approaches.

Solving the accelerator-condenser coupling problem in a nanosecond dynamic transmission electron microscope.

We describe a modification to a transmission electron microscope (TEM) that allows it to briefly (using a pulsed-laser-driven photocathode) operate at currents in excess of 10 mA while keeping the effects of condenser lens aberrations to a minimum. This modification allows real-space imaging of material microstructure with a resolution of order 10 nm over regions several microm across with an exposure time of 15 ns. This is more than six orders of magnitude faster than typical video-rate TEM imaging. The key is the addition of a weak magnetic lens to couple the large-diameter high-current beam exiting the accelerator into the acceptance aperture of a conventional TEM condenser lens system. We show that the performance of the system is essentially consistent with models derived from ray tracing and finite element simulations. The instrument can also be operated as a conventional TEM by using the electron gun in a thermionic mode. The modification enables very high electron current densities in microm-sized areas and could also be used in a nonpulsed system for high-throughput imaging and analytical TEM.

Validation and generalization of a method for precise size measurements of metal nanoclusters on supports.

We recently described a data analysis method for precise (approximately 0.1 A random error in the mean for a 200 kV instrument with a 3A FWHM probe size) size measurements of small clusters of heavy metal atoms on supports as imaged in a scanning transmission electron microscope, including an experimental demonstration using clusters that were primarily triosmium or decaosmium. The method is intended for low signal-to-noise ratio images of radiation-sensitive samples. We now present a detailed analysis, including a generalization to address issues of particle anisotropy and biased orientation distributions. In the future, this analysis should enable extraction of shape as well as size information, up to the noise-defined limit of information present in the image. We also present results from an extensive series of simulations designed to determine the method's range of applicability and expected performance in realistic situations. The simulations reproduce the experiments quite accurately, enabling a correction of systematic errors so that only the approximately 0.1A random error remains. The results are very stable over a wide range of parameters. We introduce a variation on the method with improved precision and stability relative to the original version, while also showing how simple diagnostics can test whether the results are reliable in any particular instance.

Application of image processing to STEM tomography of low-contrast materials.

In this study, the effect of various image-processing techniques on the visibility of tomographic reconstructions is investigated for a low-contrast material system of non-uniform thickness containing complex features such as grain boundaries and nanoparticles. Starting with a tilt series of high-angle annular dark-field (HAADF) images from an area of Dy-doped YBa(2)Cu(3)O(7-x)-coated superconductor obtained using a scanning transmission electron microscope, various image-processing techniques were applied. These can be classified as edge detection, contrast-enhancing methods for non-uniform thickness and image sharpening. Although the processing methods violate the projection criterion for tomographic reconstruction, they were found, at least in this case, to enhance contrast and define the correct shape and size of structural features with minimal artifacts. Enhancing the visibility of structural features in this way allows the spatial distribution of the nanoparticles, their size, number density and location relative to each other and grain boundaries to be determined, which are essential to understand the flux-pinning characteristics of these materials.

The evolution of ultrafast electron microscope instrumentation.

Extrapolating from a brief survey of the literature, we outline a vision for the future development of time-resolved electron probe instruments that could offer levels of performance and flexibility that push the limits of physical possibility. This includes a discussion of the electron beam parameters (brightness and emittance) that limit performance, the identification of a dimensionless invariant figure of merit for pulsed electron guns (the number of electrons per lateral coherence area, per pulse), and calculations of how this figure of merit determines the trade-off of spatial against temporal resolution for different imaging modes. Modern photonics' ability to control its fundamental particles at the quantum level, while enjoying extreme flexibility and a very large variety of operating modes, is held up as an example and a goal. We argue that this goal may be approached by combining ideas already in the literature, suggesting the need for large-scale collaborative development of next-generation time-resolved instruments.

Embedded nanostructures revealed in three dimensions.

Nanotechnology creates a new challenge for materials characterization because device properties now depend on size and shape as much as they depend on the traditional parameters of structure and composition. Here we show that Z-contrast tomography in the scanning transmission electron microscope has been developed to determine the complete three-dimensional size and shape of embedded structures with a resolution of approximately 1 cubic nanometer. The results from a tin/silicon quantum dot system show that the positions of the quantum dots and their size, shape, structure, and formation mechanism can be determined directly. These methods are applicable to any system, providing a unique and versatile three-dimensional visualization tool.

Enhanced current transport at grain boundaries in high-T(c) superconductors.

Large-scale applications of high-transition-temperature (high-T(c)) superconductors, such as their use in superconducting cables, are impeded by the fact that polycrystalline materials (the only practical option) support significantly lower current densities than single crystals. The superconducting critical current density (J(c)) across a grain boundary drops exponentially if the misorientation angle exceeds 2 degrees -7 degrees. Grain texturing reduces the average misorientation angle, but problems persist. Adding impurities (such as Ca in YBa2Cu3O7-delta; YBCO) leads to increased J(c) (refs 9, 10), which is generally attributed to excess holes introduced by Ca2+ substituting for Y3+ (ref. 11). However, a comprehensive physical model for the role of grain boundaries and Ca doping has remained elusive. Here we report calculations, imaging and spectroscopy at the atomic scale that demonstrate that in poly-crystalline YBCO, highly strained grain-boundary regions contain excess O vacancies, which reduce the local hole concentration. The Ca impurities indeed substitute for Y, but in grain-boundary regions under compression and tension they also replace Ba and Cu, relieving strain and suppressing O-vacancy formation. Our results demonstrate that the ionic radii are more important than their electronic valences for enhancing J(c).

Atomic scale characterization of the Pt/TiO2 interface.

We present results from an investigation of the Pt/TiO(2) catalyst system using a combination of Z-contrast imaging and electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope. Evidence of a strong interaction between the Pt particles and the support is found to be dependent on the Pt cluster size, being manifested either as an encapsulation of the Pt particles by the support or a distortion of the structure of the Pt particles. In the case of clusters that are only a few atoms in size, we show direct evidence of an epitaxial nucleation relationship between Pt and Titania. The results also show unexpectedly that Pt particles exhibit a preferential nucleation on rutile rather than anatase.

Interface structure and atomic bonding characteristics in silicon nitride ceramics.

Direct atomic resolution images have been obtained that illustrate how a range of rare-earth atoms bond to the interface between the intergranular phase and the matrix grains in an advanced silicon nitride ceramic. It has been found that each rare-earth atom bonds to the interface at a different location, depending on atom size, electronic configuration, and the presence of oxygen at the interface. This is the key factor to understanding the origin of the mechanical properties in these ceramics and will enable precise tailoring in the future to critically improve the materials' performance in wide-ranging applications.

Role of oxygen at screw dislocations in GaN.

Here we report the first direct atomic scale experimental observations of oxygen segregation to screw dislocations in GaN using correlated techniques in the scanning transmission electron microscope. The amount of oxygen present in each of the three distinct types of screw dislocation core is found to depend on the evolution and structure of the core, and thus gives rise to a varying concentration of localized states in the band gap. Contrary to previous theoretical predictions, the substitution of oxygen for nitrogen is observed to extend over many monolayers for the open core dislocation.

High temperature ferromagnetism with a giant magnetic moment in transparent co-doped SnO(2-delta).

The occurrence of room temperature ferromagnetism is demonstrated in pulsed laser deposited thin films of Sn(1-x)Co(x)O(2-delta) (x<0.3). Interestingly, films of Sn(0.95)Co(0.05)O(2-delta) grown on R-plane sapphire not only exhibit ferromagnetism with a Curie temperature close to 650 K, but also a giant magnetic moment of 7.5+/-0.5 micro(B)/Co, not yet reported in any diluted magnetic semiconductor system. The films are semiconducting and optically highly transparent.

Comparison of simulation methods for electronic structure calculations with experimental electron energy-loss spectra.

The electronic structure of hexagonal GaN is studied using two simulation techniques in order to develop a method to interpret the fine-structure of an experimental nitrogen K-edge electron energy loss spectrum obtained using a scanning transmission electron microscope. The application of these simulation methods to the bulk spectrum is a necessary first step in developing a fundamental understanding of the effect of changes in the electronic structure on the properties of defects. It is found here that both of the techniques used, multiple scattering (MS) and density functional theory (DFT), produce excellent agreement with the experimental bulk spectrum. The MS method is limited in accuracy but efficient in time, while the DFT method is more accurate but time consuming. Through the combination of these methods, experimental energy loss spectra can be readily understood, and a means to unravel the complexities of the electronic structure can be determined.